You are on page 1of 11

Journal of Applied Electrochemistry

https://doi.org/10.1007/s10800-018-1268-1

RESEARCH ARTICLE

A high-performance, disposable screen-printed carbon electrode


modified with multi-walled carbon nanotubes/graphene for ultratrace
level electrochemical sensors
Patiya Pasakon1 · Johannes Philipp Mensing1 · Ditsayut Phokaratkul2 · Chanpen Karuwan1 · Tanom Lomas1 ·
Anurat Wisitsoraat2 · Adisorn Tuantranont1

Received: 20 May 2018 / Accepted: 8 November 2018


© Springer Nature B.V. 2018

Abstract
In this work, a screen-printed carbon paste electrode (SPCE) combined with multi-walled carbon nanotubes (MCNT) and
graphene (GP) in different mixing ratios was fabricated. Electrode materials were characterized by scanning electron micros-
copy as well as Raman spectroscopy and their performance as electrochemical sensors was evaluated by cyclic voltammetry.
Results showed that SPCEs composited with 1 w% MCNT and 1 w% graphene achieved the most promising sensing perfor-
mance for ­K4FeCN6 with a sensitivity of 0.0054 µA µM−1 and limit of detection (LOD) (3S/N) at 3.1 µM. The so-prepared
electrode was then employed to detect ­H2O2 and nicotinamide adenine dinucleotide ­(NAD+/NADH) achieving sensitivity
and LOD of 0.0027 µA µM−1 and 7.1 µM for H ­ 2O2, and 0.0075 µA µM−1 and 3.6 µM for NADH, respectively. Therefore, it
was found that the addition of MCNT and graphene to commercial carbon paste for screen printable electrochemical sensor
is feasible for fabrication of sensing electrodes for electrochemical detection.
Graphical abstract 

Keywords  Screen-printed carbon paste electrode (SPCE) · Multi-walled carbon nanotube (MCNT) · Graphene (GP) ·
Electrochemical detection

1 Introduction

Recently, there have been several research works describing


the application of screen-printed electrodes (SPEs) to detect
analytes at ultratrace level in samples using electrochemical
* Adisorn Tuantranont
methods [1–4]. Some of the advantages of SPEs are portabil-
adisorn.tuantranont@nectec.or.th ity, ease of manufacture, low consumption of reagents com-
Extended author information available on the last page of the article
pared to conventional electrodes, and disposability [5–7]. In

13
Vol.:(0123456789)
Journal of Applied Electrochemistry

addition, they can be modified conveniently with sensitive with proper quantity to the carbon paste to fabricate screen-
membranes [8, 9], redox mediators, [10, 11] or enzymes printed electrodes. To do this, MCNT was added to the car-
[12, 13] to enhance specificity and sensitivity in detection bon paste to determine its optimum amount that achieved
systems. Moreover, their low cost and, thus, disposability satisfactory electrical conductivity at the lowest capacitive
make time-consuming cleaning processes for reuse obsolete. current. Following this, a small amount of GP was added to
One variety of SPEs used to detect analytes in sam- accelerate the charge transfer at the electrode surface. Over-
ples is carbon paste electrodes (CPE) [14–16]. Recently, all, the developed electrode provides clear faradaic currents
some researchers, including our group in this work, have for each analyte compared to its background current due to
attempted to increase the sensitivity and the limit of detec- its decreased capacitive current [30] which is beneficial for
tion (LOD) of CPEs by introducing conductive materials detection of analytes at ultratrace level.
in the carbon paste to fabricate as SPEs instead of using
sensitive membranes, redox mediators, or enzymes to avoid
inconstant properties and fouling of electrode surface. For 2 Experimental
instance, carbon paste can be easily mixed with graphene
powder and printed on plastic sheets to obtain screen-printed 2.1 Materials and methods
graphene electrode (SPGE) as was previously reported by us
and other groups [17–20]. Carbon rods (1/4″ diameter, Electron Microscopy Science)
Nowadays, graphene is one of the most frequently used were purchased from Becthai Company. Carbon paste and
carbon nanomaterials due to its high electrical conductiv- silver/silver chloride paste were bought from Gwent Com-
ity and large surface area compared to carbon nanotubes pany, UK. Insulating ink was purchased from Chaiyaboon
and graphite [21, 22]. Although graphene can be utilized to Brother Company, Pathumthani, Thailand. MCNT was
improve electrical conductivity of composite materials, it obtained from Chiangmai University, Thailand. Sodium
also causes a very high capacitive current of SPEs (> 1 µA). polystyrene sulfonate (PSS), ­K4FeCN6, β-nicotinamide ade-
This limits the applicability of graphene-based electrodes for nine dinucleotide, reduced dipotassium salt ­(NAD+/NADH),
monitoring analytes at ultratrace amount and with faradaic ­H2O2, ­NaH2PO4, and ­Na2HPO4 were purchased from Sigma
current to less than 1 µA. Previous reports [17–20] showed Aldrich. All chemicals were analytical grade and were used
that electrolyte solutions, measured using graphene-based without purification. Deionized water (18 MΩ∙cm) was used
electrodes, showed a very high capacitive current. This to prepare stock solutions. A MK Mini printer (Minami,
resulted in a significant decrease of faradaic current of the Japan) was employed to fabricate SPEs. Electrochemical
redox species. Therefore, analytes at ultratrace level could sensing experiments were performed using a µ-Autolab Type
not be detected if the capacitive current of the graphene- III, Metrohm, Switzerland. A Hitachi model S-4700 scan-
based electrodes is not properly reduced. ning electron microscope was employed to investigate the
In this work, a new sensing electrode was fabricated by surface morphology of each SPE. Additionally, Raman spec-
mixing carbon paste with quantities of MCNT and oxide- troscopy (NT-MDT model Ntegra spectra) was performed
free graphene to increase the electrical conductivity and to to characterize the electrodes.
decrease the peak potential of analytes. K­ 4FeCN6, ­H2O2 and
NADH (dissolved in 0.1 M pH 7 phosphate buffer solution) 2.2 Preparation of printing pastes and electrodes
were used to test the efficiency of the developed electrodes
and compare them with SPGE performance reported in our Graphene was prepared by electrolytic exfoliation. For this,
previous work. MCNT was chosen to be blended with the two carbon rods were immersed in a 3% (w/w) sodium poly-
graphene containing carbon paste, due to its excellent elec- styrene sulfonate (PSS) solution. A potential of 8 V was then
trical conductivity, large surface area, and chemical stability applied between them for 15 h leading to exfoliation of gra-
[23–25]. Furthermore, the excellent electron transfer ability phene sheets from the graphite. PSS stabilizes the dispersion
of MCNT plays an important role for electrochemical detec- and prevents restacking of graphene sheets. The graphene/
tion as confirmed by many other research works [26–29]. PSS dispersion was filtered with filter paper and washed
This article demonstrates the promising ways to utilize with ethanol and DI water several times. The collected sol-
both MCNT and graphene in the fabrication of sensing elec- ids were dried at 100 °C for 15 h and stored in a desiccator.
trodes which offer high electrical conductivity and which Figure 1 shows SEM micrographs of MCNT (Fig. 1a) and
can also detect analytes with higher sensitivity, lower LOD, oxide-free graphene (Fig. 1b) which were blended with the
and lower peak potential than SPGE. Even though, MCNT carbon paste for the fabrication of sensing electrode shown
and GP have both been widely applied as electrochemical in Fig. 2. As can be seen, MCNT features a fibrous structure
sensing materials, there is, to the best of our knowledge, no with variation of outer diameter sizes from 10 to 20 nm. The
work that explores the combined addition of MCNT and GP oxide-free graphene exhibits a two-dimensional structure

13
Journal of Applied Electrochemistry

Fig. 1  SEM micrographs of a
MCNT and b oxide-free gra-
phene synthesized by electro-
lytic exfoliation

Fig. 2  Components of fabricated electrode and electrical connectors

with sizes from 300 to 400 nm in width and length which is


in agreement with our previous work [17].
Fig. 3  Voltammograms of 0.1 M PB solution at pH 7 measured using
Printable paste was prepared by mixing commercial car- a blank SPCE, and SPCE with MCNT at 0.5%, 1%, 1.5% and 2%
bon paste with MCNT and graphene/PSS in different quanti- (w/w)
ties and dispersed homogeneously in a mortar. The pastes
were screen printed onto polyvinyl chloride (PVC) sheets
through a silk-screen printing mesh (mesh size 120 µm) over 2.3 Electrochemical sensing experiments
2 cycles. After that, Ag/AgCl ink was printed on the PVC
sheet for 2 cycles. Finally, insulating ink was printed on PVC Each fabricated electrode was cleaned to remove any con-
sheet for 2 cycles. PVC sheet was baked at 60 °C for 1 h to tamination on the surface by dropping 50 µl of 0.1 M PB
remove any solvent. solution at pH 7 on the sensing area. Cyclic voltammetry
Electrodes, as depicted in Fig. 2, consist of three screen- was used to measure the electrochemical response of the
printed parts, two carbon elements functioning as working sensors, applying a potential window ranging from 0 to
electrode (WE) and counter electrode (CE) as well as an Ag/ 1.0 V, with a scan rate of 0.1 V s−1 for 5 cycles. After the
AgCl element as reference electrode (RE). The sensing area cleaning step, only electrodes with identical voltammograms
of the electrode is defined by insulating ink screen printed were used for further testing to ensure reproducibility of the
on the PVC sheet in the final step. The surface area of the experiments.
WE is 7.68 m ­ m2. In this study, MCNT was first added to the
carbon paste in different quantities, i.e., 0.5%, 1%, 1.5%, and
2% (w/w), to choose the optimal amount for mixing with GP 3 Results and discussion
in the next step. The GP content was specifically defined
to be 0.5%, 1%, 1.5%, and 3% (w/w) to composite with the 3.1 Optimization of MCNT content
MCNT-containing carbon paste. These amounts of GP were
used in this work in order to decrease its content from 10% The voltammograms of 0.1 M PB solution at pH 7 measured
(w/w) which we previously reported in [17]. This leads to by SPCE with MCNT contents of 0.5, 1, 1.5, and 2% (w/w),
a drop in capacitive current of the sensing electrode that respectively, were investigated using cyclic voltammetry as
enhances the sensitivity and decreases the detection limit displayed in Fig. 3. Clearly, SPCEs containing excesses of
for electrochemical analysis. MCNT (1.5 and 2%) show a very high capacitive current. A

13
Journal of Applied Electrochemistry

very high capacitive current (> 1 µA) makes it impossible The modified SPCE with the best detection performance was
to detect analyte quantities at ultratrace level. Thus, only selected to detect ­H2O2 and NADH in the next step. Addi-
SPCE with 1% (w/w) MCNT was employed for compositing tionally, the detection performance of our developed elec-
with graphene/PSS since it exhibits the lowest capacitive trode was compared to that of SPCE with 10% GP (SPGE) as
current compared to other modified SPCEs. In Fig. 4a, b, reported in our previous work [17] including other relevant
SPCE with 1% MCNT and 1% GP was employed to detect works.
­K4FeCN6 to verify its performance. It was found that SPCE Figure 5 shows the surface morphologies of pure SPCE,
with 1% MCNT gave the detection sensitivity of K ­ 4FeCN6 SPCE with 1% MCNT, and SPCE with 1% MCNT and
−1
at 0.0042 µA µM . 1% GP characterized by SEM to observe the filler disper-
Subsequently, SPCE with 1% MCNT was composited sion in the carbon paste. The surface of a pure SPCE in
with GP in different amounts (0.5%, 1%, 1.5%, and 2% Fig. 5a shows large roughness after treating at 60 °C for 1 h.
(w/w)). The electrodes were then used to detect ­K4FeCN6. However, the fibrous structure of MCNT of SPCE with 1%

Fig. 4  a Voltammograms of K ­ 4FeCN6 between 10 and 1000 µM measured using SPCE with 1% MCNT and b the standard curve showing the
relation between the anodic current of ­K4FeCN6 and concentration range

Fig. 5  SEM micrographs of a a
blank SPCE, b SPCE with 1%
MCNT, and c SPCE with 1%
MCNT + 1% GP, respectively

13
Journal of Applied Electrochemistry

MCNT in Fig. 5b could not be observed in comparison to the dispersion of MCNT and GP in the carbon paste by
a pristine MCNT as shown in Fig. 1a because it was fully the raised intensity of the 2D band. For all of the elec-
covered with carbon paste. Overall, the surface morphology trodes, the D band appeared at Raman shift between 1305
of the electrode presents higher roughness due to agglomera- and 1310 cm−1, at 1577–1578 cm−1 for the G band and at
tion between MCNT particle and the carbon paste. Further- 2625–2630 cm−1 for the 2D band. However, a pure SPCE
more, MCNT also causes higher roughness of the electrode showed the highest intensity of D and G bands among
surface; thus, it should not be added to the carbon paste with all electrodes while its 2D band had the lowest intensity.
a greater amount than 1%. For SPCE with 1% MCNT and When SPCE contained 1% MCNT and 1% GP, the inten-
1% GP, MCNT and GP particles evidently do not appear sity of the 2D band was comparable to that of SPCE with
in the SEM micrograph displayed in Fig. 5c. However, its 1% MCNT and pure SPCE.
surface roughness is not as large as in SPCE samples with The results shown in Fig. 7 suggest that SPCE with
1% MCNT. This is probably due to presence of oxygen- 1% MCNT and 1% GP was the most promising elec-
containing functional groups on GP, which results in lower trode among all types due to its highest S/B ratio. As
roughness of composited ink. the results shown in Fig. 7, SPCE with 1% MCNT and
In addition, Raman spectra of pure SPCE, SPCE with 1% GP presents the greatest efficiency in detection of
1% MCNT, and SPCE with 1% MCNT and 1% GP were 1000 µM ­K4FeCN6. The reason for this is probably that
investigated and are displayed in Fig. 6. Results confirm GP has excellent electrical conductivity which will pro-
mote charge transfer at the electrode surface. Moreover,
only 1% MCNT and 1% GP can be well dispersed in the
carbon paste, which affects the highest value of S/B (20.4)
compared to other mixing ratios. In summary, SPCE with
1% MCNT and 0.5% GP is not sufficiently efficient for
electrochemical detection. Meanwhile, both 1.5% and 2%
GP may be an excessive amount, which causes the large
agglomeration of fillers in the carbon paste and higher
peak potential of analytes. Therefore, SPCE with 1%
MCNT and 1% GP (from here on denoted SPCE/CNT1%/
G1%) is the most promising electrode and was also applied
for detection of H
­ 2O2 and NADH in the following study to
verify its detection performance.

Fig. 6  Raman spectrum of (a) a blank SPCE, (b) SPCE with 1%


MCNT, and (c) SPCE with 1% MCNT and 1% GP, respectively

Fig. 7  a Comparing the anodic current signal (S) of 1000 µM ­K4FeCN6 measured by SPCE with 1% MCNT after mixing GP at 0.5%, 1%, 1.5%,
and 2% (w/w) and b the ratio of S/B of each electrode

13
Journal of Applied Electrochemistry

3.2 Electrochemical performance of developed


electrode

The detection performance of SPCE/CNT1%/G1% compared


to SPCE with 1% MCNT, and a pure SPCE was tested
with 1000 µM analytes of K ­ 4FeCN6, ­H2O2, and NADH as
illustrated by their voltammograms in Figs. 8, 9, and 10.
It was found that SPCE/CNT1%/G1% can clearly increase
the anodic current of analytes (~ 6 µA for ­K4FeCN6 and
~ 7.5 µA for NADH) after background current subtrac-
tion in comparison to SPCE with 1% MCNT (~ 4  µA

Fig. 9  Voltammograms of 1000 µM ­H2O2 measured by a SPCE with


1% MNCT and 1% GP, b SPCE with 1% MCNT and c a blank SPCE

for ­K4FeCN6 and ~ 6.4 µA for NADH) and a pure SPCE


(~ 3 µA for ­K4FeCN6 and ~ 6 µA for NADH). For ­H2O2
detection, its voltammogram between 0.6 and 1.0 V rises
significantly for SPCE/CNT1%/G1% as compared to SPCE
with 1% MCNT, and a pure SPCE. This result indicates
that both MCNT and GP promote electron transfer ability
and electrical conductivity for detection of H ­ 2O2. How-
ever, the anodic current of ­H2O2 at 0.9 V after background
­ 4FeCN6 measured by a SPCE
Fig. 8  Voltammograms of 1000  µM K
with 1% MNCT and 1% GP, b SPCE with 1% MCNT, and c a blank subtraction using SPCE with 1% MCNT (~ 1.3 µA) and a
SPCE pure SPCE (~ 1.5 µA) is not obviously different. Therefore,

13
Journal of Applied Electrochemistry

3.3 Effect of scan rate

The objective of this study is to estimate the dynamic prop-


erty of SPCE/CNT1%/G1% by measuring 1000 µM K ­ 4FeCN6,
­H2O2, and NADH at various scan rates of 20, 50, 80, 100,
120, 150, 180, 200, 220, and 250 mV/s. It was found that the
change of the anodic current amplitude of NADH depends
considerably on the scan rate as depicted in Fig. 11c. The
high anodic current change also meant the highest sensitivity
(0.6457 µA/(mV S−1)1/2) among all analytes (Fig. 11d). For
1000 µM ­K4FeCN6, its redox reaction moderately responses
towards an increment of the scan rate as the sensitivity
(0.4722 µA/(mV S−1)1/2) displayed in Fig. 11a and d. In con-
trast, a rise of scan rate affects the anodic current increased
slowly of ­H2O2 as shown in Fig. 11b from the sensitivity
(0.265 µA/(mV S−1)1/2) reported in Fig. 11d.
To conclude, an increase of the scan rate increased the
current linearly for all analytes. However, the scan rate of
100 mV/s was chosen for the following studies because this
scan rate the standard curve plotted between the anodic cur-
rent of analytes and the scan rate ranging 20–250 mV/s. On
the other hand, the scan rate at very high speed (> 100 mV/s)
will also involve the higher peak potential of redox species.
Thus, an eligible scan rate should provide both a higher cur-
rent and lower peak potential of analytes.

3.4 Effect of analyte concentration

SPCE/CNT1%/G1% was utilized to detect K ­ 4FeCN6, ­H2O2,


and ­NAD+/NADH in a wide dynamic range (10–1000 µM)
and resulting voltammograms are shown in Fig. 12a–c. The
experiments achieved satisfying results since the developed
electrode clearly proved the detection of these analytes.
The results showed that the developed electrode could be
successfully applied to monitor analytes. Finally, the per-
formance of this electrode with regard to the detection
of ­K4FeCN6, ­H2O2, and NADH was compared to that of
SPGE as summarized in Table 1. The detection sensitivity
Fig. 10  Voltammograms of 1000  µM NADH measured by a SPCE of ­K4FeCN6, ­H2O2, and NADH, as reported in Fig. 12d, is
with 1% MNCT and 1% GP, b SPCE with 1% MCNT, and c a blank 0.0054 µA µM−1, 0.0027 µA µM−1, and 0.0075 µA µM−1,
SPCE, respectively respectively.
Overall, SPCE/CNT1%/G1% gives the greater analytical
performance in comparison to SPGE due to lower peak
SPCE composited with both MCNT and GP materials is potential, higher sensitivity, and lower detection limit for
required for electrode fabrication to detect ­H2O2. On the ­K4FeCN6 (3.1 µM), H ­ 2O2 (7.1 µM), and NADH (3.6 µM) as
other hand, SPCE/CNT1%/G1% can distinctly decrease the summarized in Table 1. A proper decrease of GP content in
peak potential of anodic current, namely 0.29–0.31 V for the carbon paste resulted in reducing the capacitive current
­K4FeCN6 and 0.4–0.45 V for NADH, respectively, which of sensing electrode and affects a rise of the faradaic cur-
will be highly useful for electrochemical detection com- rent of redox species. Furthermore, the linear range of ­H2O2
pared to SPCE with 1% MCNT and a pure SPCE. Further- (10–1000 µM) and NADH (10–1000 µM) measured by the
­ 2O2 in biosensing
more, it can also be employed to detect H developed electrode was significantly less than the results
systems which peroxide oxidase enzyme is coated on the obtained with SPGE, namely 3650–6150 µM for ­H2O2 and
working electrode [31–33]. 70–7700 µM for NADH.

13
Journal of Applied Electrochemistry

Fig. 11  Voltammograms of a 1000 µM ­K4FeCN6, b 1000 µM ­H2O2, and c 1000 µM NADH measured by different scan rates (20–250 mV/s), as
well as d the standard curve plotted between the anodic current (µA) of each analyte and the scan r­ ate1/2 (mV S−1)1/2

In addition, the developed electrode promoted the elec- by electrode modification to increase the selectivity to ana-
tron transfer ability of analytes. This result is affirmed by lytes of interest.
the peak potential decreased of ­K4FeCN6 (0.29–0.31 V),
­H2O2 (0.8–0.85  V), and NADH (0.45–0.5  V) compared 3.5 Repeatability and reproducibility study
to inkjet-printed GP-PEDOT:PSS electrode employed to
detect ­K4FeCN6 (0.3–0.42 V), ­H2O2 (0.8–1.0 V), and NADH The repeatability of SPCE/CNT1%/G1% was evaluated by
(0.6–0.65 V) as studied from another previous work of our recording cyclic voltammogram for 10 successive cycles.
group [34]. From the results, our electrode still reserved the stability
Overall, ­K4FeCN6, ­H2O2, and NADH are common ana- towards the oxidation of each analyte up to 10 successive
lytes that can be detected using our developed electrode. The cycles with relative standard deviation (RSD, n = 10), such
results suggest that this electrode could be also employed as 5.25% for ­K4FeCN6, 7.26% for ­H2O2, and 3.70% for
to monitor other analytes. However, the performance of NADH. Moreover, the reproducibility for electrochemical
this developed electrode on the detection of real samples detection was estimated from 10 electrodes. It was found
will have to be further studied by sample pretreatment or that the developed electrode exhibited a good reproducibility

13
Journal of Applied Electrochemistry

Fig. 12  Voltammograms of a ­K4FeCN6, b ­H2O2, and c NADH measured using SPCE with 1% MCNT and 1% GP, and d their standard curve
plotted between the anodic current and concentration range between 10 and 1000 µM

(RSD, n = 10), namely 10.39% for ­K4FeCN6, 8.71% for only SPCE/CNT1%/G1% is greatly useful to increase sensi-
­H2O2, and 3.39% for NADH, respectively. tivity and to decrease LOD (3S/N) of analyte detection.
Most importantly, the developed electrode is able to detect
­K4FeCN6, ­H2O2, and NADH with lower peak potential and
4 Conclusions lower linear range (10–1000 µM). Therefore, our work is a
beneficial guidance to apply the advantages of both MCNT
In this work, SPCE/CNT1%/G1% exhibited a very good per- and GP materials in the fabrication of screen-printed elec-
formance towards electrochemical detection for K
­ 4FeCN6, trode for electrochemical detection.
­ AD+/NADH among all electrodes. Interestingly,
­H2O2, and N

13
Journal of Applied Electrochemistry

Table 1  Data from comparing the performance of SPCE with 1% MCNT and 1% GP, and the previous works

SPCE with 1% MCNT and 1% GP K4FeCN6 CV 10–1000 3.1 µm This work


NADH 10–1000 3.6 µm
H2O2 10–1000 7.1 µm
Screen-printed graphene electrode (SPGE) K4FeCN6 CV 5–320 µm 4.2 µm [17]
NADH 70–7700 µm 26 µm
H2O2 3650–6150 µm 379.28 µm
Graphene-PEDOT:PSS-modified SPCE K4FeCN6 CV 0.5–320 µm 0.36 µm [34]
NADH 50–1500 µm 17.28 µm
H2O2 1.3–7.6 mM 194.37 µm
Inkjet-Printed Carbon Nanotube ink on paper Fe2+ Potential step voltammetry 10 µm–0.2 mM 10 µm [35]
Al2O3-GO nanocomposite-modified electrode NADH DPV 30–330 µm 4.5 µm [36]
CV
Reduced graphene oxide and poly (allylamine hydrochloride) NADH DPV 0.05–5 mM 6.6 µm [37]
on SPCE
MWCNTs/AuNPs/poly-neutral red (PNR) film-modified NADH Amperometry 12.4–150 µm 3.72 µm [38]
SPCE
Inkjet-printed Prussian blue (PB) film-modified SPCE H2O2 Chronoamperometry 0.02–0.7 mM 0.02 mM [39]
Pt-MWCNT-modified SPCE H2O2 Chronoamperometry 1–15 mM 10 µM [40]
0.1–1 mM
10–100 µM

Acknowledgements  The authors are grateful for the research grant for sensor based on an electropolymerized metal organic framework.
project (P1851485) from National Electronics and Computer Technol- Toxins 7:3540–3553. https​://doi.org/10.3390/toxin​s7093​540
ogy Center (NECTEC), National Science and Technology Develop- 8. Shoukry AF, Badawy SS, Issa YM (1987) Diphenhydramine-sen-
ment Agency (NSTDA), and from Thailand Research Fund for TRF sitive membrane electrodes based on poly(vinylchloride) matrices
Research Team Promotion Grant (RTA6180004). and their use in drug analysis. J Electroanal Chem Interfacial Elec-
trochem 233:29–36. https:​ //doi.org/10.1016/0022-0728(87)85003​
-9
9. Hosseini M, Sadeghi HB, Rahimi M et al (2009) Highly selective
and sensitive tin(II) membrane electrode based on a new syn-
References thesized schiff’s base. Electroanalysis. https​://doi.org/10.1002/
elan.20080​4485
1. Ricci F, Amine A, Palleschi G, Moscone D (2003) Prussian Blue 10. Morita M, Kitamura S, Ishikawa M, Matsuda Y (1996) Immobi-
based screen printed biosensors with improved characteristics of lization of a cerium redox mediator on a glassy carbon electrode
long-term lifetime and pH stability. Biosens Bioelectron 18:165– for electroorganic reactions. Electroanalysis 8:826–830. https​://
174. https​://doi.org/10.1016/S0956​-5663(02)00169​-0 doi.org/10.1002/elan.11400​80823​
2. Ben Rejeb I, Arduini F, Arvinte A et al (2009) Development 11. Karimi-Maleh H, Keyvanfard M, Alizad K et al (2012) Electrocat-
of a bio-electrochemical assay for AFB1 detection in olive oil. alytic determination of glutathione using multiwall carbon nano-
Biosens Bioelectron 24:1962–1968. https​://doi.org/10.1016/j. tubes paste electrode as a sensor and isoprenaline as a mediator.
bios.2008.10.002 Int J Electrochem Sci 7:6816–6830
3. Ping J, Wu J, Wang Y, Ying Y (2012) Simultaneous determination 12. Banitaba MH, Davarani SSH, Mehdinia A (2011) Study of inter-
of ascorbic acid, dopamine and uric acid using high-performance actions between DNA and aflatoxin B1 using electrochemical and
screen-printed graphene electrode. Biosens Bioelectron 34:70–76. fluorescence methods. Anal Biochem 411:218–222. https​://doi.
https​://doi.org/10.1016/j.bios.2012.01.016 org/10.1016/j.ab.2011.01.007
4. Li M, Li Y-T, Li D-W, Long Y-T (2012) Recent developments 13. Scott DA, Skillen AW (1992) Amperometric enzyme electrode for
and applications of screen-printed electrodes in environmen- NADH detection employing co-immobilized lactate dehydroge-
tal assays—a review. Anal Chim Acta 734:31–44. https​://doi. nase and lactate oxidase. Anal Chim Acta 256:47–52. https​://doi.
org/10.1016/j.aca.2012.05.018 org/10.1016/0003-2670(92)85324​-Y
5. Wu K, Fei J, Bai W, Hu S (2003) Direct electrochemistry of DNA, 14. Pauliukaite R, Metelka R, Švancara I et al (2002) Carbon paste
guanine and adenine at a nanostructured film-modified electrode. electrodes modified with B ­ i2O3 as sensors for the determination
Anal Bioanal Chem 376:205–209. https​://doi.org/10.1007/s0021​ of Cd and Pb. Anal Bioanal Chem 374:1155–1158. https​://doi.
6-003-1887-0 org/10.1007/s0021​6-002-1569-3
6. Zhang X, Li C-R, Wang W-C et al (2016) A novel electrochemical 15. Pekec B, Oberreiter A, Hauser S et al (2012) Electrochemical
immunosensor for highly sensitive detection of aflatoxin B1 in sensor based on a cyclodextrin modified carbon paste electrode
corn using single-walled carbon nanotubes/chitosan. Food Chem for Trans-resveratrol analysis. Int J Electrochem Sci 7:4089–4098
192:197–202. https​://doi.org/10.1016/j.foodc​hem.2015.06.044 16. Cheraghi S, Taher MA, Fazelirad H (2015) Voltammetric deter-
7. Jiang M, Braiek M, Florea A et al (2015) Aflatoxin B1 detection mination of silver with a new multi-walled carbon nanotube
using a highly-sensitive molecularly-imprinted electrochemical

13
Journal of Applied Electrochemistry

modified paste electrode. Russ J Electrochem 51:271–277. https​ 29. Wang J, Musameh M (2003) Carbon nanotube/teflon com-
://doi.org/10.1134/S1023​19351​41100​32 posite electrochemical sensors and biosensors. Anal Chem
17. Karuwan C, Wisitsoraat A, Phokharatkul D et al (2013) A dis- 75:2075–2079
posable screen printed graphene–carbon paste electrode and its 30. Zheng D, Vashist S, Dykas M et al (2013) Graphene versus multi-
application in electrochemical sensing. RSC Adv 3:25792. https​ walled carbon nanotubes for electrochemical glucose biosensing.
://doi.org/10.1039/c3ra4​4187c​ Materials 6:1011–1127. https​://doi.org/10.3390/ma603​1011
18. Antiochia R, Gorton L (2014) A new osmium-polymer modi- 31. Roopa RA, Mantelingu K, Rangappa KS, Kamara MN (2016)
fied screen-printed graphene electrode for fructose detection. Development of novel bienzymatic assay for quantification of
Sens Actuators B Chem 195:287–293. https​://doi.org/10.1016/j. glucose in human serum. Asian J Pharm 10:170–176
snb.2014.01.050 32. Garg B, Bisht T, Ling Y-C (2015) Graphene-based nanomateri-
19. Cruys-Bagger N, Tatsumi H, Borch K, Westh P (2014) A graphene als as efficient peroxidase mimetic catalysts for biosensing appli-
screen-printed carbon electrode for real-time measurements of cations: an overview. Molecules 20:14155–14190. https​://doi.
unoccupied active sites in a cellulase. Anal Biochem 447:162– org/10.3390/molec​ules2​00814​155
168. https​://doi.org/10.1016/j.ab.2013.11.024 33. Darabdhara G, Sharma B, Das MR et al (2017) Cu-Ag bimetallic
20. Randviir EP, Brownson DAC, Metters JP et al (2014) The fabrica- nanoparticles on reduced graphene oxide nanosheets as peroxidase
tion, characterisation and electrochemical investigation of screen- mimic for glucose and ascorbic acid detection. Sens Actuators B
printed graphene electrodes. Phys Chem Chem Phys 16:4598. Chem 238:842–851. https​://doi.org/10.1016/j.snb.2016.07.106
https​://doi.org/10.1039/c3cp5​5435j​ 34. Sriprachuabwong C, Karuwan C, Wisitsorrat A et al (2012) Inkjet-
21. Punckt C, Pope MA, Liu J et al (2010) Electrochemical perfor- printed graphene-PEDOT:PSS modified screen printed carbon
mance of graphene as effected by electrode porosity and graphene electrode for biochemical sensing. J Mater Chem 22:5478. https​
functionalization. Electroanalysis 22:2834–2841. https​://doi. ://doi.org/10.1039/c2jm1​4005e​
org/10.1002/elan.20100​0367 35. da Costa TH, Song E, Tortorich RP, Choi J-W (2015) A paper-
22. Bao C, Guo Y, Song L, Hu Y (2011) Poly(vinyl alcohol) nano- based electrochemical sensor using inkjet-printed carbon nano-
composites based on graphene and graphite oxide: a compara- tube electrodes. ECS J Solid State Sci Technol 4:S3044–S3047.
tive investigation of property and mechanism. J Mater Chem https​://doi.org/10.1149/2.01215​10jss​
21:13942. https​://doi.org/10.1039/c1jm1​1662b​ 36. Mekawy MM, Hassan RYA, Ramnani P et al (2018) Electro-
23. Ahammad AJS, Lee J-J, Rahman MA (2009) Electrochemical sen- chemical detection of dihydronicotinamide adenine dinucleotide
sors based on carbon nanotubes. Sensors 9:2289–2319. https:​ //doi. using ­Al2O3-GO nanocomposite modified electrode. Arab J Chem
org/10.3390/s9040​2289 11:942–949. https​://doi.org/10.1016/j.arabj​c.2018.03.017
24. Bandaru PR (2007) Electrical properties and applications of car- 37. Istrate O-M, Rotariu L, Bala C (2016) Electrochemical determina-
bon nanotube structures. J Nanosci Nanotechnol 7:1239–1267. tion of NADH using screen printed carbon electrodes modified
https​://doi.org/10.1166/jnn.2007.307 with reduced graphene oxide and poly(allylamine hydrochlo-
25. Santhanam KSV, Sangoi R, Fuller L (2005) A chemical sensor ride). Microchim Acta 183:57–65. https​://doi.org/10.1007/s0060​
for chloromethanes using a nanocomposite of multiwalled carbon 4-015-1595-4
nanotubes with poly(3-methylthiophene). Sens Actuators B Chem 38. Sahin M, Ayranci E (2015) Electrooxidation of NADH on modi-
106:766–771. https​://doi.org/10.1016/j.snb.2004.09.034 fied screen-printed electrodes: effects of conducting polymer
26. Mohan S, Okumu F, Oluwafemi O et al (2016) Electrochemical and nanomaterials. Electrochim Acta 166:261–270. https​://doi.
behaviour of silver nanoparticle-MWCNTs hybrid nanostruc- org/10.1016/j.elect​acta.2015.03.030
tures synthesized via a simple method. Int J Electrochem Sci 39. Hu J-Y, Lin Y-P, Liao Y-C (2012) Inkjet printed Prussian blue
11:745–753 films for hydrogen peroxide detection. Anal Sci Int J Jpn Soc Anal
27. Zhao T, Liu L, Li G et al (2012) Preparation and electrochemical Chem 28:135–140
property of CMC/MWCNT composite using ionic liquid as sol- 40. Chou T-C, Wu K-Y, Hsu F-X, Lee C-K (2018) Pt-MWCNT
vent. Chin Sci Bull 57:1620–1625. https​://doi.org/10.1007/s1143​ modified carbon electrode strip for rapid and quantitative detec-
4-012-5009-2 tion of H­ 2O2 in food. J Food Drug Anal 26:662–669. https​://doi.
28. Tsierkezos NG, Ritter U, Thaha YN, Downing C (2015) Applica- org/10.1016/j.jfda.2017.08.005
tion of multi-walled carbon nanotubes modified with boron oxide
nanoparticles in electrochemistry. Ionics 21:3087–3095. https​://
doi.org/10.1007/s1158​1-015-1496-x

Affiliations

Patiya Pasakon1 · Johannes Philipp Mensing1 · Ditsayut Phokaratkul2 · Chanpen Karuwan1 · Tanom Lomas1 ·


Anurat Wisitsoraat2 · Adisorn Tuantranont1

1 2
Graphene and Printed Electronics Research Team (GPE), Opto‑Electrochemical Sensing Research Team (OEC),
National Electronics and Computer Technology Center National Electronics and Computer Technology Center
(NECTEC), 112 Thailand Science Park, Phahonyothin Road, (NECTEC), 112 Thailand Science Park, Phahonyothin Road,
Khlong Neung, Khlongluang, Pathumthani 12120, Thailand Khlong Neung, Khlongluang, Pathumthani 12120, Thailand

13

You might also like